Coal liquefaction process

ABSTRACT

A PROCESS IS DISCLOSED FOR DE-ASHING AND LIQUEFYING COAL WHICH COMPRISES CONTACTING COMMINUTED COAL WITH WATER, AT LEAST A PORTION OF WHICH IS IN THE LIQUID PHASE, A REDUCING GAS AND A COMPOUND SELECTED FROM AMMONIA AND CARBONATES AND HYDROXIDES OF ALKALI METALS, AT LIQUEFACTION CONDITIONS, INCLUDING A TEMPERATURE OF 200-370*C. TO PROVIDE A HYDROCARBONACEOUS PRODUCT.

United States Patent C 3,796,650 COAL LIQUEFACTION PROCESS Peter Urban,Northbrook, Ill., assignor to Universal Oil Products Company, DesPlaines, Ill. No Drawing. Filed July 24, 1972, Ser. No. 274,145 Int. Cl.Cg 1/00, 1/06' U.S. Cl. 208-10 5 Claims ABSTRACT OF THE DISCLOSURE Aprocess is disclosed for de-ashing and liquefying coal which comprisescontacting comminuted coal with water, at least a portion of which is inthe liquid phase, a reducing gas and a compound selected from ammoniaand carbonates and hydroxides of alkali metals, at liquefactionconditions, including a temperature of 200-370 C. to provide ahydrocarbonaceous product.

BACKGROUND This invention relates to a process for convertingcarbonaceous solids to more valuable hydrocarbonaceous products. Morespecifically, this invention relates to a process for de-ashing andconverting coal to hydrocarbon products by contacting the coal withliquid water, a compound selected from ammonia and hydroxides andcarbonates of alkali metals, and a reducing gas at particularliquefaction conditions to provide the hydrocarbon products.

Several methods for converting coal to more valuable liquid orliquefiable products are known to the art. One method employsdestructive distillation of the coal. More recently, high pressurehydrogenation and solvent extraction techniques have been employed. Oneof the more onerous difliculties encountered in prior coal liquefactionart is the separation of the liquefied hydrocarbonaceous products fromthe unconverted coal, ash, and various solid inorganic materialsinvariably contained in the raw coal. Under typical prior artliquefaction conditions, the solids are dispersed in the liquefiedmaterial and in the organic solvent, if one is used, in a finely dividedparticulate state, rendering separation extremely diflicult. Settling,centrifuging and filtration techniques have been employed with somesuccess, but are economically unattractive as a means for de-ashing theliquefied materials.

The product of coal liquefaction typically requires further treatment bytechniques analogous to petroleum refining methods in order to convertthe liquefaction product into valuable liquid hydrocarbons such asgasoline, or to provide benzene and other organic chemicals. Thisfurther treatment generally comprises catalytic hydrogenation andcracking of the hydrocarbonaceous tars that result from liquefaction. Ithas been found that, in general,

the particulate matter must be removed from the liquefaction productbefore such further treatment can effectively and economically beundertaken. Consequently, the prior art has concentrated on methods foreconomically separating ash from the liquefaction product. The processof this invention at least partially obviates the need for suchseparation techniques, by reducing the ash content of the liquefactionproduct to such a low level that further catalytic treatment of theliquefaction product can be undertaken directly without furtherseparation of solids.

Another major drawback of prior art coal liquefaction methods has beenthe requirement for large amounts of hydrogen both in high pressurehydrogenation and in solvent extraction. It has been suggested that thisproblem can be overcome by converting only that small fraction of thecoal which is relatively rich in hydrogen. It is obviously moredesirable to convert as large a fraction as possible of the coal tovaluable products. A process which 3,796,650 Patented Mar. 12, 1974could employ a low cost substitute for hydrogen or substantially reducethe amount of hydrogen needed would be economically more attractive thanprior art methods and would constitute a significant advancement.

SUMMARY An object of the present invention is to provide a novel processfor the liquefaction of carbonaceous solids to produce more valuablehydrocarbonaceous products.

A further object of the present invention is to provide an improvedprocess for liquefying coal, utilizing liquid phase water and a readilyavailable reducing gas, to produce valuable hydrocarbonaceous products.

A particular object of the present invention is to provide a process forliquefying coal in which the ash content of the product is reduced,resulting in a hydrocarbonaceous product of greater utility.

In an embodiment, the present invention relates to a process forconverting a solid carbonaceous material to a hydrocarbonaceousliquefaction product which comprises the steps of: (a) contacting saidsolid material with a reducing gas, with water, at least a portion ofwhich is liquid, and with a catalytic compound selected from ammonia,alkali metal hydroxides and alkali metal carbonates, at liquefactionconditions including a temperature of about 200 C. to about 370 C. and apressure sufiicient to maintain said water at least partially in theliquid phase; and (b) recovering said hydrocarbonaceous product from theresulting mixture.

In a more limited embodiment, the present invention relates to a processfor converting a solid carbonaceous material to a hydrocarbonaceousliquefaction product which comprises the steps of: (a) contacting saidsolid material with a reducing gas, with water, at least a portion ofwhich is liquid, and with a catalytic compound selected from ammonia,alkali metal hydroxides and alkali metal carbonates, at liquefactionconditions including a temperature of about 200 C. to about 370 C. and apressure sutficient to maintain said water at least partially in theliquid phase; (b) separating the resulting mixture into an aqueous phaseand a hydrocarbonaceous phase; and (c) recovering said liquefactionproduct from said hydrocarbonaceous phase.

I have discovered that coal and other carbonaceous solid materials canbe liquefied to produce valuable hydrocarbonaceous products -by treatingthe coal with a relatively large quantity of water which is at leastpartially in the liquid phase, and with a reducing gas and a compoundselected from ammonia and hydroxides and carbonates of alkali metals. Ihave found that the ash content of the coal can thereby be reducedsignificantly and that the hydrocarbonaceous product can be furtherprocessed catalytically, in a manner analogous to petroleum refiningmethods, without the necessity of removing ash and undissolvedcarbonaceous materials. In place of the hydrogen employed in prior art,coal liquefaction methods, carbon monoxide, or a mixture of carbonmonoxide with hydrogen, provides an effective reducing gas in thepresent process, permitting the use of low cost sources of reducing gas,e.g. synthesis gas.

PREFERRED EMBODIMENT The carbonaceous solid materials which can beutilized in the present process to provide the hydrocarbonaceous productinclude any sort of coal, lignite, peat, oil shale, tar sand or similarsubstance. The preferred carbonaceous solid is a bituminous coal. Forexample, an Illinois Bellville District stoker coal having a moistureand ash free volatile content of greater than about 20% or higher issuitable. Although not essential to the process, it is preferred thatthe carbonaceous solid to be employed in the process is first reduced toa particulate, comminuted form. Preferably, the

carbonaceous solid is ground or pulverized to provide particlessufficiently small to pass through a 100 mesh Tyler sieve or smaller.Coal ground sufiiciently to pass through a 200 mesh sieve isparticularly preferred.

The alkali metal compounds which can be employed in the present processinclude sodium hydroxide, potassium hydroxide, sodium carbonate, sodiumhydrogen carbonate, potassium carbonate, potassium hydrogen carbonate,potassium sodium carbonate, or a mixture of two or more of the above.Similar salts of other alkali metals such as lithium or rubidium canalso be employed, but not necessarily with equivalent results. The abovenoted sodium salts are preferred, particularly sodium carbonate andsodium hydrogen carbonate.

Ammonia can be employed in place of the foregoing alkali metalcompounds. Nitrogen-containing organic compounds can also be utilized toprovide ammonia by decomposition. Suitable organic compounds includehexamethylene tetramine, formamide, ammonium acetate, guanidine, biuret,and ammonium salts of phenolic acids such as phenol, resorcinol, etc.

The reducing gas employed in the present process may be pure hydrogen orpure carbon monoxide. A mixture of these gases is also suitable. Thereducing gas may be commingled with one or more gases or vapors whichare relatively inert in the liquefaction reaction, including nitrogen,carbon dioxide, etc. One convenient, suitable source of the reducing gasis a synthesis gas produced by reaction of carbon or hydrocarbons withsteam to produce carbon monoxide and hydrogen. A variety of methods forproducing a synthesis gas suitable for use in the present process areknown in the art.

Liquefaction conditions, in the present process, include a temperatureof about 200 C. to about 370 C. and a pressure at least sufficient toprovide a liquid water phase at the desired temperature. For example, inan operation wherein it is desired to maintain a temperature of about200 C., a pressure of at least about 20 atmospheres is maintained. Athigher temperature operations, e.g., 350- 370 C., a pressure of about135 atmospheres to about 220 atmospheres or more is maintained. Bestresults are achieved when a temperature of about 250 C. to about 350 C.is employed. It is also preferred to employ pressures below about 400atmospheres.

The amount of water contacted with the carbonaceous solid atliquefaction conditions is between about -100 wt. percent and about 1000wt. percent of the carbonaecous solid. Good results are obtained whenthe amount of water is between about 100 wt. percent and about 300 wt.percent of the carbonaceous solid. The amount of ammonia or alkali metalcompound contacted with the solid is sufiicient to provide aconcentration of about 0.1 wt. percent to about 1000 wt. percent. Aconcentration of about 0.1 wt. percent to about 200 wt. percent, basedon the carbonaceous solid, is preferred. Ammonia or the alkali metalcompound may conveniently be employed as an aqueous solution of, forexample, ammonium hydroxide, sodium carbonate, etc., in the watercomponent. When this method is employed, it is preferred to maintain aconcentration of about wt. percent or more of the ammonia or alkalimetal compound in solution. The superatmospheric pressures employed atliquefaction conditions in the present process may be wholly supplied bythe reducing gas, or may be supplied, in part, by inert gases, watervapor, etc. In any case, the partial pressure of the reducing gas 1smaintained at least about 10% of the total pressure. The amount of thereducing gas employed is about 0.5 s.c.f. to about 175 s.c.f. per poundof carbon in the carbonaceous solid to be processed. Preferably, theamount of the reducing gas utilized is about s.c.f. to about 75 s.c.f.per pound of carbon in the solid.

The process of the present invention may be employed in a batch typeoperation or a continuous type operation. When a batch operation isemployed, fixed amounts of the carbonaceous solid, water, theammonia-producing compound or alkali metal compound and the reducing gasare charged to a suitable liquefaction zone, such as a rockingautoclave. The reactants are contacted in the liquefaction zone for aperiod of time sufiicient to produce the desired amount of conversionand then the products are withdrawn from the liquefaction zone and thedesired hydrocarbonaceous product is separated and recovered. A suitablecontact time in a batch type operation is about 1 minute to about 600minutes, preferably about 200 minutes to about 400 minutes. In acontinuous operation, the carbonaceous solid, water, theammonia-producing compound and the reducing gas are continuously chargedto a suitable liquefaction zone and contacted therein. The reactionproducts are continuously withdrawn from the reactor and the desiredhydrocarbonaceous product is separated and recovered. A suitable liquidhourly space velocity in a continuous type operation (volume of thereactor divided by the total volume of reactants charged per hour) ofabout 0.16 to about 1.0 may be employed, and about 0.5 to about 0.25 isparticularly preferred.

The liquefaction zone or reactor utilized in the present process may beany suitable vessel or reactor which can maintain the reactants atsuflicient temperature and pressure to provide liquefaction conditions.For example, a conventional rocking autoclave is a suitable reactor foruse in a batch type operation. A variety of suitable vessels for use asthe reactor are known in the art of coal liquefaction. Preferably, theliquefaction zone includes means for admixing the reactants by stirringor other agitation.

The mixture recovered after the liquefaction step, in addition to thedesired hydrocarbonaceous product, 'will contain water, which willgenerally be in a separate phase from the product. Most of the solidsremaining in the mixture will be found in the water phase. Thus, thehydrocarboneacous product may conveniently be separated from the waterand from at least a major portion of any remaining solid residualmaterials such as ash, by simple mechanical separation of the phases.The water phase thus recovered may be recirculated to the liquefactionstep for further use. Similarly, reducing gas which is not consumedduring the liquefaction step may be recovered and recirculated to theliquefaction step. I have found that the present process actually doesnot consume hydrogen or carbon monoxide in substantial amounts, so thatlittle fresh reducing gas is normally required in a continuousoperation. The hydrocarbonaceous product may be further processed, forexample, by petroleum refining methods such as cracking, to providehydrocarbon fuels, aromatic chemicals for petrochemical uses, etc. Whenthe process herein disclosed is utilized to treat the preferredcarbonaceous solid, bituminous coal, the hydrocarbonaceous productrecovered comprises a tarry material which is liquid at about C. and hasan ash content significantly lower than that of the raw bituminous coal.One of the major problems encountered in prior art coal liquefactionprocesses has been the separation of ash from the hydrocarbonaceousmaterials produced. The present process reduces the amount of ash in thehydrocarbonaceous liquefaction product sufiiciently that furtherseparation of solids may not be necessary, particularly since much ofthe solid residue remains in the water phase and is consequently veryeasily removed. This is particularly advantageous in 'view of the priorart methods which use a hydrocarbonaceous solvent in the liquefactionstep, resulting in high contamination of the solvent with ash and othersolids.

Liquefaction conditions may include the use of various catalysts tofurther enhance the liquefaction reactions in the present process.Suitable catalysts include metals from Group VIH of the Periodic Tableof the Elements, particularly the sulfides of these metals, especiallyiron sulfide, nickel sulfide and cobalt sulfide. The above-noted metalsulfide catalysts may be utilized at a concentration of about 0.001 wt.percent to about wt. percent of the amount of carbonaceous solidmaterial to be treated. A preferred concentration for such catalysts isabout 0.1 wt. percent to about 2 wt. percent of the carbonaceous solid.In general, a catalyst may be employed by admixing it with thepulverized coal as a solid.

The hydrocarbonaceous product recovered from the liquefaction step is atarry material melting at about 50 C. to about 200 C. comprising about80-85 wt. percent carbon and about 6.5-8 wt. percent hydrogen, which ispreferably further treated by conventional petroleum refining methods toprovide hydrocarbon products. One particularly convenient method forrecovering valuable components in the liquefaction product andsimultaneously removing any remaining ash, carbonaceous solids, etc., isby extracting the hydrocarbonaceous product with an organic solvent. Thesolvents which may te employed are well known in the art. Examples ofsome suitable solvents which are particularly preferred include benzene,toluene, xylene, and similar C C aromatics, hexane, heptane and similarC C parafiins, ketones, C -C2 cycloparaffins and alkylcycloparafiins,etc. Extraction conditions generally include a temperature of about 30C. to about 300 C. and preferably about 50 C. to about 150 C.Superatmospheric pressure is desirable but not essential. After acontact time of about 0.1 minute to about 1500 minutes, the solvent andthe product materials dissolved therein are mechanically or otherwiseseparated from whatever solid materials remain at the extractionconditions employed. The soluble hydrocarbons are then recovered byfractionation of the solvent or other conventional methods.

The following examples illustrate various embodiments and advantages ofthe process of the present invention. The examples are not intended tolimit the broad scope of the present invention, and many otheradvantages and embodiments of the invention will be apparent to thoseskilled in the art from the description provided herein.

EXAMPLE I A seam coal from Randolph Co., Bellville District, 111., wasanalyzed to determine its average composition, which was found to be asshown in Table I.

The coal was pulverized to provide particles sufficiently small to passthrough a 200 mesh Tyler screen. One hundred grams of the pulverizedcoal and 400 grams of water were placed in an 1850 cc. rockingautoclave. The autoclave was sealed and sufficient hydrogen wasintroduced to provide a pressure of 70 atmospheres. No ammonia, alkalimetal hydroxide or alkali metal carbonate was utilized. The contents ofthe autoclave were heated to a temperature of 350 C. A pressure of 310atmospheres in the autoclave was observed. The contents were agitated at350 C. for 6 hours, and then the autoclave was cooled to roomtemperature. The pressure was observed to be 62 atmospheres. The excesspressure was released and the remaining contents of the autoclave wereremoved. The effluent from the autoclave was observed to consist of awater phase and a hydrocarbonaceous phase. The hydrocarbonaceous phase,which solidified at about 100 C., was separated from the water phase bysimple decantation and dried. The hydrocarbonaceous materials were thenextracted with benzene. It was found that the benzene soluble fractionof the hydrocarbonaceous phase contained 30 wt. percent of the carbon inthe original grams of coal charged to the autoclave.

EXAMPLE II One hundred grams of the same pulverized coal employed inExample I was placed in the same autoclave used in Example I. No waterand no salts were employed in this run. One hundred cc. of xylene wasplaced in the autoclave with the coal and the autoclave was sealed.Sufficient hydrogen was charged to the autoclave to produce a pressureof 70 atmospheres. The contents of the autoclave were agitated at atemperature of 350 C. for six hours. The contents were then cooled andthe excess pressure was released. After separation of the xylene solventfrom the hydrocarbonaceous product and drying, the product was extractedwith benzene in a manner identical to that used in Example I. It wasfound that 31 wt. percent of the carbon in the original 100 gramscharged to the autoclave had been converted to benzene solublehydrocarbons.

EXAMPLE III In order to demonstrate the superiority of the process ofthe present invention over the methods employed in Examples I and II,100 grams of the pulverized coal described in Example I was placed inthe same autoclave. Four hundred cc. of water and 50 grams of sodiumhydrogen carbonate were also placed in the autoclave. The autoclave wassealed and sufficient hydrogen was introduced to raise the pressure to70 atmospheres. The contents of the autoclave were then stirred at 350C. for six hours, after which the autoclave was cooled and excesspressure was released. The benzene soluble product, recovered in exactlythe same manner as employed in the foregoing Examples I and II was foundto contain 48 wt. percent of the carbon in the 100 grams of coaloriginally charged to the autoclave. From comparison of Example IH withExamples I and II it is apparent that the presence of both water and thealkali metal salt is necessary to attain a high degree of conversion aswas achieved in Example HI. For instance, the method of the presentinvention, employed in Example III produced 37% greater conversion thanExample I where no alkali metal salt was used and produced 35% greaterconversion than the method of Example II where no water was used.

EXAMPLE IV The following procedure was employed to demonstrate thesubstantially equivalent results obtained when ammonia was substitutedfor the alkali metal carbonate employed in Example III. Fifty grams ofthe pulverized coal used in Example I was placed in an 850 cc. rockingautoclave with 100 cc. of water and 100 cc. of a 28% ammonium hydroxidesolution. The autoclave was sealed and sufficient carbon monoxide wasintroduced to provide a pressure of 70 atmospheres. The contents of theautoclave were heated to 350 C. and agitated at that temperature for 6hours. The pressure was observed to be 410 atmospheres. The autoclavewas then cooled to room temperature and the excess pressure released.The remaining contents were removed and the water phase thereof wasseparated by decantation. The hydrocarbonaceous phase was dried andextracted with benzene. The benzene soluble hydrocarbons were found tocontain 45 wt. percent of the carbon in the coal originally charged tothe autoclave, or slightly less than was obtained using sodium hydrogencarbonate as in Example III. The yield obtained using ammonia comparedvery favorably to the yields of Examples I and II, achieving 33% greaterconversion and 31% greater, respectively, than these two runs.

EXAMPLE V Having shown by Examples I through IV that the presence ofwater and an alkali metal salt or ammonia is essential to obtain thedesired conversion, and that the presence of an organic solvent, as inExample II, did not effect the conversion significantly, a run wasundertaken to demonstrate that the presence of a reducing gas was alsoessential. Fifty grams of the coal described in Example I was charged tothe autoclave used in Example IV along with 100 cc. of water and 100 cc.of the same 28% ammonium hydroxide solution utilized in Example IV.Without introducing any reducing gas, the autoclave was sealed and thecontents were agitated and heated to 350 C. The pressure observed was202 atmospheres. After 6 hours the autoclave was cooled and the contentswere removed. The water phase was separated by decantation, and thehydrocarbonaceous product was dried and extracted with benzene as inExample IV. It was found that only wt. percent of the carbon in theoriginal charge of coal to the autoclave was present in the benzenesoluble product. The necessity for employing a reducing gas in theprocess of the present invention is apparent from this result.

EXAMPLE VI In order to demonstrate the efficiency of a mixture ofhydrogen and carbon monoxide as the reducing gas in the present process,the following operation was performed. Fifty grams of the pulverizedcoal described in Example I were placed in the autoclave described inExample IV. One hundred cc. of the 28% aqueous ammonium hydroxidesolution were also charged to the autoclave. The autoclave was sealedand suflicient carbon monoxide was charged to the autoclave to provide apressure of 35 atmospheres. Sutficient hydrogen was then charged toprovide a hydrogen partial pressure of 35 atmospheres and a totalpressure of 70 atmospheres. The contents of the autoclave were heated to350 C., and a pressure of 388 atmospheres was observed. The contents ofthe autoclave were maintained at 350 C. and agitated for six hours,after which the contents of the autoclave were cooled to roomtemperature and excess pressure released. The contents of the autoclavewere removed and decanted into a water fraction and a hydrocarbonaceousfraction. The hydrocarbonaceous fraction was dried and extracted withbenzene. The extracted materials were found to contain 43% of the carbonin the coal originally charged to the autoclave.

Use of a hydrogen-carbon monoxide mixture Provided a conversion ofsubstantially the same degree as the use of pure hydrogen or pure carbonmonoxide.

EXAMPLE VII In order to demonstrate further the desirability ofutilizing water in the liquid phase, an operation was undertaken using amixture of hydrogen and carbon monoxide at lower pressure. One hundredgrams of the pulverized coal described in Example I was charged to the1850 cc. rocking autoclave along with 100 cc. of water and 100 cc. ofthe 28% ammonium hydroxide solution. The autoclave was sealed andsufiicient hydrogen and carbon monoxide were introduced to provide 10atmospheres partial pressure of each gas, with a total pressure of 20atmospheres. The contents of the autoclave were agitated at 350 C. for 6hours, after which the autoclave was cooled to room temperature andexcess pressure was released. The contents of the autoclave were removedand the water phase was separated by decantation. The bydrocarbonaceousphase was dried and extracted with benzene. It was found that only 11wt. percent of the carbon in the original charge of coal to theautoclave had been recovered in the benzene soluble fraction.

EXAMPLE VIII In order to demonstrate the non-equivalence of salts of thealkali metals other than carbonates and hydroxides, the followingoperation was undertaken using sodium sulfate. One hundred grams of thepulverized coal described in Example I was placed in the 1850 cc.rocking auto clave, and cc. of water, 100 grams of Na SO and 100 cc. ofxylene were also charged. The autoclave was sealed and pressured withhydrogen to 70 atmospheres. The contents of the autoclave were agitatedat 350 C. for 6 hours and then the autoclave was cooled to roomtemperature and excess pressure was released. The contents were removedand the water phase separated by decantation. The hydrocarbonaceousphase was dried and extracted. The benzene soluble hydrocarbons werefound to contain 26 wt. percent of the carbon originally charged to theautoclave in the coal. It is apparent from the low conversion achievedusing sodium sulfate, that it is not equivalent to the carbonate saltemployed in Example III or to ammonia as employed in Example IV.

EXAMPLE IX The following operation was undertaken to determine theelfect produced by using an organic solvent, in this case xylene, withthe water, ammonia and reducing gas.

In two separate operations, 100 grams of the pulverized coal describedin Example I were placed in the 1850 cc. rocking autoclave. 100 cc. ofwater, 100 cc. of an aqueous 28% solution of ammonium hydroxide and 100cc. of xylene were also charged to the autoclave in both runs. Theautoclave was then sealed. In the first run, sufiicient hydrogen wasintroduced to increase the pressure to 70 atmospheres. In the secondrun, sufficient carbon monoxide was charged to provide 70 atmospherespressure. The contents of the autoclave were heated to 350 C. in bothruns. A pressure of 246 atmospheres was observed in the run usinghydrogen, and a pressure of 316 atmospheres was observed in the runusing carbon monoxide. The contents of the autoclave were agitated for 6hours at 350 C. in both runs. The autoclave was then cooled to roomtemperature and the excess pressure released. The remaining contentswere removed and decanted into a water fraction and a hydrocarbonaceousfraction. The hydrocarbonaceous fraction was dried and solvent extractedwith benzene. In the run using hydrogen as the reducing gas, theextracted materials contained 46 wt. percent of the carbon in theoriginal 100 grams of coal charged to the autoclave. In the run usingcarbon monoxide, 45 wt. percent of the original coal carbon wascontained in the extracted material. The foregoing demonstrates thatusing an aromatic hydrocarbon solvent has substantially no effect on thedegree of conversion achieved using the process of the presentinvention.

The foregoing examples clearly demonstrate the superior conversionachieved using the processing conditions and components of the presentinvention, and indicate a preferred mode of operation of the presentprocess when a batch reaction scheme is employed. Modification of theoperation to a continuous type operation, etc., will be obvious to thoseskilled in the art.

I claim as my invention:

1. A process for de-ashing and liquifying coal which comprisescontacting the coal with from about 100 wt. percent to about 1000 wt.percent of water, a reducing gas selected from the group consisting ofhydrogen, carbon monoxide and a mixture of hydrogen and carbon monoxide,and a catalytic compound selected from the group consisting of ammoniaand alkali metal hydroxides and carbonates at a temperature of fromabout 200 C. to about 370 C. and a pressure of at least about 20atmospheres but below about 400 atmospheres and sulficient to maintainsaid water at least partially in the liquid phase, separating theresultant mixture into a hydrocarbonaeeous phase and a solids-containingaqueous phase, and recovering a hydrocarbon liquefaction product fromsaid hydrocarbonaceous phase.

2. The process of claim 1 wherein the liquefaction product is recoveredfrom said hydrocarbonaceous phase by solvent extraction.

3. The process of claim 1 wherein said catalytic compound comprisesabout 0.1 wt. percent to about 1000 wt. percent of said coal and saidalkali metal is selected from sodium and potassium.

4. The process of claim 1 wherein said reducing gas 5 compriseshydrogen.

5. The process of claim 1 wherein said reducing gas comprises carbonmonoxide.

References Cited UNITED STATES PATENTS 2/1972 Seitzer 20810 8/1972Seitzer 208-40 DELBERT E. GANTZ, Primary Examiner V. OKEEFE, AssistantExaminer

